Resin composition



Patented Jam 16, l t

nnsm coMrosrrioN Henry A. Gardner, Chevy Chase, Md., and ArnoldKirkpatrick, St. Louis, Mo., assignors to Monsanto Chemical Company, St.Louis, Mo.,

a corporation of Delaware 1 No Drawing. Original application June 11,1935, Serial No. 26,034. Divided and this application November 29, 1937,Serial No. 177,154

9 Claims. (01. 260-42) This application is a division of our copendingacids tend to impart objectionable tastes or odors application, SerialNumber 26,034, filed June 11, to the material, either immediately uponincor- 1935, which has issued as Pat. No. 2,121,028. In poration, orafter aging. For this latter reason our said copending application wehave described the modified resins are not entirely satisfactory usesfor certain new resin compositions and have for coating wrappingmaterials for food products.

claimed such uses. The present application deals The present inventionis based upon the disspecifically with the compositions per'se. coverythat alkyd typ r sin a n d by c The main objects of the invention are toprodensation or reaction of a dihydric alcohol and a vide plastic andfilm-forming compositions which polycarboxylic acid, as above described,may be 10 are highly resistant to water, moisture and other combinedwith resins obtained by the interaction 10 permeating fluids, which arehighly soluble in of an aromatic sulfonamid and an aldehyde to mostorganic solvents, and, readily compatible /obtain products which possessexcellent solubility with cellulosic compositions and other plastic fandcolor characteristics, and which are other-- 1 materials, which are oflight color, and do not wise substantially free from the objectionablereadily discolor under the action of ultra-violet features heretoforeencountered in .connection light, which adhere firmly and permanently toWith alky y r si smooth, glossy surfaces, which form solutions The prepa the component resins of relatively low viscosity and may, therefore,be prising the ne ma may proceed in Convenof high concentration, whichare non-toxic, tional manner. For example, the dihydric alcotastelessand odorless, and do not become rancid ols, Such as ethyl e lyc p y y 20upon aging, and which are especially suitable for butylene glycol orglycol ethers, such as diethcoating wrapping materials for foodproducts. ylene glycol or other dihydric alcohols maybe These and otherobjects will become apparent mp oy d. hese d y alcohols y be duponperusal of the appended specification. mixed with each other or withother polyhydric It has heretofore been proposed to prepare compounds,such as glycerol. The polycarboxylic 25 artificial resins of theso-called alkyd typeby acid, or preferably its anhydride, such asphthalic condensing a polyhydric alcohol, such as glycerol anhyd de, a de dlhydrle alcohols, are merely or glycol, with a polycarboxylic acid orpreferably heated together in suitable proportions to a. the anhydrideof such acid. Among the acids fairly high temperature. The preparationof the so the anhydrides of which have been proposed for reactionproduct oi aromatic sulfcnamid and so "this purpose, are phthalic acid,succinic acid, it the aldehyde m y d in accordance with ,maleic acid,adipic acid, citric acid, etc. 111- the disclosures of German Patent359,675 or though these compositions possess many virtues, :369,644,Which Contain descriptions of a p a i y they are, in some respects, notentirely satisface s o this yp example'of a material tory' for certainpurposes. For. example, their which is available in quantities upon themarket-3 a with other lacquer materials, such as cellulose utility inthe preparation of lacquers and varand w ich may b employed to furnishthe eldenishes is restricted because of their relatively low hydearomatic sulf nam d a i n r duct. thus solubility in most common organicsolvents, and, obviating the necessit 0 preparing this tebecause oftheir relatively slight compatibility a s that s d under the trade name.santclite compositions, including nitrocellulose, cellulose In heincorpo ation of the resins into each acetate, benzyl and benzoylcellulose, etc. They e t yd resin is preferably maintained are also of apronounced brownish color and frein a relatively fluid condition by hean it t a quently of high acid number, which tends to re temperature ofapproidm t ly 2 0 C. The aroduce their value for many purposes. maticsulfonamid-aldehyde reaction product is 45 I has heretofore beenproposed to obviate merely incorporated thereinto and the material thesedifficulties by incorporating into the resins is allowed to stand at arelatively h gh temperaa fatty acid such as oleic acid, stearic acid,ture tor a short period of time. A su table ricinoleic acid, or oilscomprising .the glycerldes 'of plasticizer may a so b ineerporoted a s tme these acids. However, complete compatibility 01' into the compo t InView the remarkable the fatty acid or the glyceride thereof with thesolubility characteristics of the material, practiresin israther'difiicult of attainment. Further- ;cally any of the conventionalplasticizers may be more, this addition of fatty acid or fatty acidemployed, and selection of one of satisfactory Jglyceride does notimprove the color characterischaracteristics is largely determined bythe ma'- tics of the material, and it is also round that the tonal intowhich the composition is to be inoor- I5 porated. For example, if it isto be combined with cellulose compositions, a plasticizerwhich is also asatisfactory plasticizer for the cellulose material should be selected.An example of a 6 plasticizer which is eminently suitable for use inmost compositions containing the newresin, is methyl phthalyl ethylglycolate. Other esters of ,phthalyl glycolate, including the butyl andpropyl iesters, may also be employed for many purposes. 10 However,these latter plasticizers are not particularly satisfactory if thecomposition is designated for admixture with cellulose acetate, but withnitrocellulose they are quite satisfactory. These compositions are ofthe general formula:

COOS-Ham COOCHaCOOCJIam m where n is any whole number. Otherplasticizers, such as toluenesulfonamid and dibutyl or diethylphthalate, camphor, etc. may also'be employed if desired.

The new resin compositions may be incorpogg rated with almost any of thecommon organic solvents; examples of the latter include methyl, ethyl,propyl, butyl, and amyl alcohols, diacetone alcohol; ketones, suchasacetone; .esters such as ethyl or methyl acetate; and hydrocarbons, such39 as toluene and benzene, if incorporated with a acetate, may alsobeemployed as solvents. Compositions obtained' by addition of a solventmay be employed directly as lacquers, or they may be as admixed withmany of the common cellulose compositions, including nitrocellulose,cellulose acetate and benzyl and benzoyl cellulose, with which materialsthe new resin is highly compatible. The cellulose material, when thusmodified, is characterized by an unusual degree of resistance tocharacterized by, substantially complete lack of odor and theydo notcontain any fatty acids 6 which are subject to decomposition upon aging.'For that reason cellulosic compositions, such as cellulose acetate,containing the new resins as modifiers, are highly suitable for use inthe preparation of compositions for coating paper or similar materialemployed in wrapping cigarettes and food products.

An excellent wrapping material for foods may be obtained by coatingregenerated cellulose, such as the product sold under the trade name ofor spraying with cellulose acetate, or cellulose nitrate containing aresin prepared in accordance with the provisions of this invention. Thecomposition adheres firmly and permanently to the I a regeneratedcellulose sheets and imparts-thereto a most unusual degree of resistanceto water, moisture and other permeating fluids. to test the resistanceto water of the coating material, a sheet of untreated "Cellophane wasstretched over the bottom of a tube .and a few crystals of a watersoluble dye placed upon the top thereof. The end of the tube covered bythe 'Cellophane was then immersed in water and within a period of thirtyseconds suillcient mois- 70 ture had permeated through themembrane tocause the dye to run and thus to discolor the supporting film. On theother hand, similar sheets of treated Cellophane? which were coated witha lacquer composition prepared in accordance u with the provisions ofthis invention were found small amount (-15%) of an ester, such asethyl- I water and moisture, as well as vapors such as may be emitted byfood products. They are also Cellophane"-upon one or both sides bydipping In order to be entirelyresistant to permeation by water, evenafter a period of immersion of twenty-four hours, or more.

In the preparation of the resins constituting the subject matter of thisinvention glycol has 5 been suggested as constituting a suitablepolyhydric alcohol and phthalic anhydride as constituting a satisfactorypolycarboxylic acid for the preparation of the alkyd resin. It is to beunderstood that glycerol admixed with glycol or 10 diethylene glycol maybe employed in lieu of ethylene glycol. However, products obtained fromthese polyhydric alcohol mixtures are somewhat less satisfactory thanthose obtained from ethylene glycol. Anyof the aromatic sulfonamids maybe employed to react with an aldehyde to form the second component ofthe resin material. Examples of such sulfonamids are ortho, meta or paratoluene sulfonamid, simple phenyl sulfonamid, xylyl sulfonamid, etc. Asexamples of aldehydes which may be reacted with these sulfonamidproducts may be mentioned formaldehyde, acetaldehyde, furfuraldehyde, aswell as other materials containing the reactive methylene group, such asparaldehyde, hexamethylenetetra- 9 mine, etc.

The following constitutes a specific example of the preparation of amaterial in accordance with the provisions of the present invention.Phthalic anhydride in the ratio by weight of '15 parts is incorporatedwith ethylene glycol in the ratio of parts, and heated to a temperatureof 240 C. At this point 5 additional parts of ethylene glycol are addedand heating is continued at a temperaturerange of 240-250 C. for 35 aperiod of about thirty minutes. The product is then allowed to coolapproximately to 200 C. at which point grams of para-toluenesulfonamid-aldehyde resin, prepared in accordance with any of theexamples of the German patents above referred to, or if preferred, acommercial product such as Santolite'Ml-IP is added. The temperature of200 C. is maintained for ten minutes, at the end of which time there isadded 50 grams of methyl phthalyl ethyl glycolate, or any otherconventional plasticizer, and the temperature is then maintained at -160C. for a further period of ten minutes. The resultant resin will befound to have the extremely low acid value of about 15 and will be foundto be quite soluble in any of the ordinary organic solvents, such asacetone, alcohols, esters of alcohols, ketones, toluol or xylol. Theproportions, temperature and periods of time above given are notcritical, but are merely exemplary, and may be varied over a wide range.

' The material is highly compatible with most cellulose materials,including even cellulose acetate which is compatible with butrelativelyv few materials. For example, ordinary alkyd resins w areincompatible with cellulose acetate. However, when they are combinedwith aromatic sulfonamid resins in accordance with the provisions of thepresent invention, they become readily compatible and the resin itselfexerts a pronounced plasticizing action upon the cellulosic material.The following is a typical formula of a cellulose composition containingthe new e Partsby weight Nitrocellulose 8 10 Resin prepared inaccordance with the example Butyl acetate 20 Ethyl Acetate Toluol parentthat resins prepared in accordance with.

the provisionsof this invention are characterized by unusual solubilityand compatibility characteristics and possess an unusual number ofadditional highly desirable characteristics. For this a reason they arehighly valuable as commercial products. Although we have described onlythe preferred embodiments of the invention, it will be apparent to thoseskilled in the'art that the invention is mited to these specific formsand that numerous modifications may be made therein without departurefrom the spirit of the invention or the scope of the appended claims.

What we claim is:

1. As a new composition of matter a resin com patible with celluloseesters comprising the reaction product of the alkyd resin obtained byreaction of phthalic anhydride, and a mixture of polyhydric alcoholsofwhich the predominant constituents are dihydric alcohols, a phthalateester of a monohydric alcohol which is compatible with said alkyd resinand a condensation product 01' an aromatic solfonarnid with an aldehyde.

2. As a new composition of matter a resin compatible with celluloseesterscomprising the reaction product of the alkyd resin obtained byreaction of phthalic anhydride and a dihydric alcohol, a phthalate esterof a monohydric alcohol which is compatible with said alkyd resin and acondensation product of an aromatic sulfonamid with an aldehyde.

3. A composition of matter as defined in claim .esterisanallwl thereaction product of the 1 and furtber characterized i that the phthalatephthalyl alkyl glycolate.

. 4. .A composition of matter as defined in claim 1 and furthercharacterized in that the aromatic suli'onamid condensation product isone resulting from the interaction of toluene suli'onamid andformaldehyde.

5. A composition of matter consisting 01 a resin compatible withcellulose esters and comi prising the reaction product of the alkydresin obtained by reaction of phthalic anhydride and a dihydricalcohoLanialkyl phthalyl alkyl glycolate which compatible withsaid alkydresin and a condensation product of an aromatic sulfonamid with analdehyde.

6. A composition of matter consisting of a resin compatible withcellulose esters and comprising the reaction product of the alkyd resinobtained by reaction of phthali'c anhydride and a dihydric alcohol, aphthalate-ester consisting of methyl pythalyl ethyl glycolate and acondensation product or an aldehyde.

7. A composition of matter resin compatible with cellulose prising thereaction product of obtained by reaction of phthalic anhydride and adihydric alcohol, a phthalate ester 01' a monohydric alcohol which iscompatible with said consisting of a esters and comalkyd resin and acondensation product oi. toluene sulfonamid with formaldehyde.

8. A composition of matter consisting of a resin compatible withcellulose esters and comprising alkyd resin obtained by reaction ofphthalic anhydride and a mixture of polyhydric alcohols of which thepredominant constituents are dihydric alcohols, a phthalate esterconsisting of methyl phthalyl ethyl glycolate and a condensation productof anaromatic sulfonamid with an aldehyde.

9; A composition of matter consisting of a'resin compatible withcellulose esters and comprising the reaction product of the alkyd resinobtained by reaction of phthalic anhydride and ethylene glycol, aphthalate ester consisting of methyl phthalyl ethyl glycolate and acondensation product of toluene sulfonamid with formaldehyde.

' HENRY A. GARDNER.

ARNOLD KIRKPATRICK aromatic sulfonamid with an 25 a the alkyd resin

